Condensation products of the phenol-formaldehyde type



Patented June 13, 1939 232.112 l CONbENSATION raonucrs 0F 'rna rna vnor-roamnnnrna TYPE Herbert Hiinel, Vienna, and AloisZinke, Graz,

' Austria, assignors to Helmuth Reichhold, Dee

. troit,-Mich., doing business as Reiehholdflhemicals NoDrawing rial No.111,490. 1935 The invention relates to high-grade condensa tion productsof the phenol-formaldehyde type According to our new processv there maybe produced valuable bases for the manuiacture of varnishes .and alsoproducts which may be employed tor various other purposes, for examplefor the manufacture. of plastic masses or shaped bodies and the like.

The present invention is a continuation in part of our applicationSerial No. 30,152, filed ,6, 1935. 1 l

In our application Serial No. 30,152 the production of resinouscondensation products is described, phenols, terpenes and compoundsclosely related therewith and aldehyd'es being used as startingmaterials. First there are produced more or less high molecular phenolicbodies by condensing terpenes and the like with'phenols with the aid ofsuitable catalysts or using separately formed derivatives asintermediates according to various methods, preferably however byforming terpene halides and then condensing the same withphenols withthe aid or metal halides.- These phenolic bodies having substituents ofterpene-like nature are then subjected to condensation with compoundscontaining a carbonyl group, preferably after having been suitablypurified. Products of the most various properties are obtained by thesecondensation reactions according to the conditions of thereactions andto the proportions of the components,

Now we have iound addition to terpenes, terpenogenes, correspondingoxygen-containing compounds, acyclic con '1.

pounds genetically related to the terpenes, etc.

plication SeriahNo. 30,152 there may be used as starting materials quitegenerally alicyclic compounds having side chains or joined onnonaromatic rings or technical mixtures containing at least aconsiderable proportion of such compounds. From phenols and thesestarting 'ma terials preferably bymeans of their halogen compoundsequally valuable more or less'high' molecular phenolic bodies areobtained having properties similar to those of the phenolic bodiesobtained from theterpene like substances. structure of thephenolic bodyfirst formed is thus characterised in that alicyclic compounds carryside chains or joined on non aromatic rings on the onehand and at leastone aromatic substituent having at least one'phenolic hydroxyl group onthe other hand. If the alicyclic compound carries a-plurality of sucharomatic subthatinstead of and in pounds such as naphthenic alcoholsobtained from naphthenic The Application November18, 1936, Se-

In Germany November 21,

' ecuims. (ct 260-51) stituents these are linked with different C-atomsof the alicyclic compound. I

The alicyclic compounds or technical mixtures containing the same may beof saturated or un saturated nature. They may be oxygen-free oroxygen-containing i. e. they may be both hydrocarbons and e. g. alcoholsand the like.

The formation of the halogen compounds of these starting materials ofcourse must be in agreement with the nature of these starting materials.If essentially saturated compounds (bydrocarbons) are used, such ashexahydrotoluene,

hexahydroxylene, dekahydronaphthalene, or generally speaking homologuesof the cyclohexane or other polymethylene compounds i. e. cyclo-.parafilnes (cyclopentane, -heptane etc), substitution of halogen is'necessary, Very cheap technical mixtures of substances being rich insuch saturatedcompounds are e.-g'. mineral oils, rich in naphthenes, ofCaucasian, Rumanian and partly also Galician, Californian and Canadianorigin, more particularly the middle or heavy benzines' obtained fromthe mineral oils; Also brown coal tars and mineral coal tars and theirdistillation products respectively contain such acyclic compounds. Otherexamples for suitable saturated compounds are: methylcyclobutane,

diand tri-methylcyclohe'xanes contained in petroleum fractions,;di-methylethylcyclohexanes, methylcyclopentane, dicyclopentyl and.derivatives isolated e. g. by Jennings, La., dicycloheptyl,

dekanaphthenes or also oxygen containing'commethylcyclopentanoL--hexanol,

methylcyclopentene, methylenecyclopentane, ethylidencyclop'entane,dicyclopentadie'ne, tetrahy-u.

drotoluene, methylenecycloheptane;methylcycloheptene, hexaandoctohydronaphthalene, etc.

"Some relatively low molecular mixtures of substances :which may beobtained from high molecular substances partly systematically (e. g;

the starting magasolines' produced by cracking), partly as other 1 oils)form particularly cheap starting materialswise almost valueless byproducts (e. g. coal w having a large content of. such unsaturatedhydrocarbons.

In addition to employing halogen compounds ,as intermediates thesestarting materials may also be condensed with phenols according tometals and metalloids e. g. aluminium-chloride,

ferric chloride, boron fluoride, and in certain cases also silicatedearths. The condensation" is however most suitably effected in thepresence of metal halides using hydrogen halide addition products asintermediates.

Starting materials having alcoholic groups may either be first treatedwith hydrogen halide in order to obtain by esterification thecorresponding halogen compounds, which are then condensed with phenolsin the way described hereinbefore; or they may also be reacted as such-with phenols by means of dehydrating agents with the formation of(substituted) relatively high molecular phenollc bodies.

'Ihe formation of the relatively high molecular phenolic bodies with theuse of halides of the alicyclic substances as intermediates is. as arule, to be preferred 1, si'nce..this method may be generally employed,irrespective whether there are unsaturated or alcoholic groups present;2. since almost without exception C--C linkages are formed whencondensing with phenols, i.- e. substitution of nuclear hydrogen atomsof the phenol takes place, but no sub- I stitution' of .the hydrogenatom of the phenolic tained therefrom with formaldehyde and the, likerespectively are distinguished by the fact.

hydroxyl group with the formation of etherlike compoundm also theformation of disturbing by-products may be avoided in all cases.Moreover it is possible to form intermediates relatively rich in halogenby substitution, which when condensed with phenols yield high molec ularbodies carrying a correspondingly large amount of phenolic rings.

One often succeeds in limiting the substitution by halogen to tertiarilybound hydrogen atoms which are presentin the alicyclic compounds at theplaces where the side-chains branch off. The corresponding tertiaryhalides not only particularly readily react with phenols but also thesubstitution of thephenols as a rule takes place in p-position to. thephenolic hydroxyl group. particularly when employing low reactiontemperatures. P-substituted phenolic bodies and the condensationproducts obthat they do not show yellowing phenomena. In order to beable selectively to effect the substitution of hydrogen atoms of thealicyclic starting materials or generally in order to secure an as faras possible uniform halogenation it is suitable to work e. g. whenchlorina'ing at low temperatures with strong dilution and exposure toactinic light rays.

Among alcoholic starting materials in an analogousway tertiary alcoholsare to be preferred.

among unsaturated starting materials those which contain groups whereinolefinic linkages are present at one or several branching places. (Inthe case of intermediary addition of hydrogen halide, sulphuric acid,etc. there are also formed tertiary compounds.)

Moreover we should like to mention that in order to obtain suitablehalogen compounds in accordance with the nature of the starting materialseveral diflerent methods may be employed simultaneously orsubsequently, e. g. addition (ofihalogen or hydrogen halide) andsubstitution or esterification (hydrogen by halogen or hydroxyl byhalogen) the latter by means of hydrogen halide. Depending on the choiceof the reaction conditions the most various phenolic bodies and mixturesthereof respectively may be produced. They are of oily or soft nature ifnon-unitary mixtures of substances are used as starting materials whichpredominantly contain monovalent halides or form the same intermediaryin the reaction mixture. -If unltary, more particularly tertiarymonohalides have'been employed, suitably obtained in the mannerdescribed hereinbefore. crystalline well defined phenolic bodies may beproduced. If essentially. polyvalent halides or compounds forming thesame are employed, as a rule, more or less solid, tack-free, resinousmasses are obtained. When starting from these substances it is oftenpossible also to convert reaction masses which are first oily or softresinous (viscous) into solid resinous phenolic bodies by prolongedheating in the presence of a catalyst and the hydrogen halide set freeduring the reaction. An increase of the molecular weight takes placeduring the heating which is probably due to polymerisation caused byunsaturated linkages still present or formed.

To condense the herein phenolic bodies with formaldehyde, similarprincipals apply to those set forth in our application Ser. No. 30,152.When condensing highly viscous or solid resinous phenolic bodies theco-employment oi' indiiferent solvents of the phenolic body isadvisable, e. g. of benzene hydrocar alcohol or the coemployment of lowmolecular phenols. The use of such auxiliary materials is particularlyadvisable in the case of a preferred mode of effecting the condensationof the high molecular phenolic body with formaldehyde, which consists inthat the two substances are caused to act on each other in the presenceof strong alkalies at ordinary or only slightly increased temperaturefor a prolonged period in a given case for several days. In most casesonly this method permits of compounding excess of formaldehyde(calculated on bound. phenol) and in this way leads, to distinctlyhardenable condensation products. Particularly when it is intendedlateron to employ the condensation products in the varnish manufacturethe alkali is precautiously eliminated. i As to the uses of the productsobtainer according to the various condensation methods herein described,attention is called to the disclosure of our application Ser. No.30,152. Also the new products described herein constitute valuable basicmaterials for the varnish manufacture as well as for the production ofplastic masses and .of molded articles respectively if desired with theaddition of various filling materials.

Example 1 Dry chlorine is passed into 50 grms. of benzine having aboiling range of 96 to 1 04 C. and ob- 7 tion of 1 gm. of anhydrous zincchloride" After tained from Rumanian petroleum, under cooling with waterand exposure to actinic light rays, until the amount of chlorineabsorbed amounts to 19 grms.

The resulting chlorinated product is condensed at 50 C. with 50 grms. ofphenol with the addiheating for 24 hours the reaction product is treatedwith steam and the excess phenol removed in this manner. The gross yieldof condensation product amounts to 50 guns. The product consists forthe, greater part of p-tert.-

methyl-cyclohexylhenol which may be obtained pure by vacuum distillationand re-crystallisw tion from ligroin.

Both the entire condensation product and also in particular the purifiedproduct yield on condensation with formaldehyde very valuablenonyellowing resins readily soluble in oils. Ahardenable oil-solubleresin may for example be obtained by condensing 1 part of thecrystalline product with 0.8 part of aqueous formaldehyde (40% vol.)with aid of soda lye or the like. After acidifying there is obtained atordinary temperaw ture an oily condensation product which is viscons athigher temperatures and which on further heating becomes solid andresinous. The resulting products are for example also readily soluble inbenzine and the like. Instead of the benzine mentioned which contains aconsiderable portion "of methylcyclohexane, there may also be employedas starting material the pure hydrocarbon obtained by hydrogenation oftoluene.

Example 2 100 arms. of benzine rich a boiling range of (SB-88 C. aresubjected under cooling with water and exposure to actinic light rays tothe action of dry chlorine until an increase in weight of 43 grms. hastaken place. The resulting halide is then condensed at to 70 C. with 85grms. of phenol and 5 guns. of anhydrous zinc chloride. After heatingfor 24 hours the reaction product is treated with steam and the excessphenol is removed.

The crude product is a darkyiscous substance which on being condensedwith formaldehyde with the aid of catalysts, constitutes valuable highmolecular oil-soluble resins.

Example 3 A mixture of xylenols catalytically hydrogenated by means ofhydrogen (1 part) is brominated with elementary bromine (3 parts). Thereaction is promoted by exposure to actinic light rays and by heatingabove 100 C.

The reaction product is gradually introduced into 3 parts of moltenphenol wherein 0.1 part of anhydrous zinc chloride and a small portionof anhydrous ferric chloride are dissolved. Alter the condensationreaction is terminated at 40 C.

the catalysts are'rendered inactive by addition of water and the excessof phenol employed is removed in a" suitable way. The residue (2 /2parts) constitutes a thickly liquid, light brown mass which ran not bedistilled without decomposition.

' "When condensed with 0.5 to 0.! part formaldehyde (40% vol.) atboiling temperature with the aid of strong mineral acids as catalyst ahard .resin. light brown in color and readily soluble in oils isobtained. The condensation is advantageously carriedout in the presenceof an indifferent solvent, for example toluene.

in naphthenes with Example 4 The entire mixture of the phenolic bodiesobtained according to Example 3 is condensed with 3 parts offormaldehyde (40% vol.) during 14 days in the presence of 0.2 part ofsodium hydroxide which cause a clear solution. The alkali is thereafterprecautiously removed, e'. g. by acidifying. The thickly liquidcondensation product which is rather light in color. may be converted byprecautiously heating into a solid, tough resin which issoluble 10? onlyin alcohols but also in benzene hydroca bons. 13y heating under pressureat temperatures above 130 C. an unmeltable insoluble turnable mass isobtained in a short time which is distinguished by good light fastness,very great resistance against chemical influences, e. g. alkalies. Afurther advantage consists in that the condensation product iscompatible with considerably larger proportions of a plasticizer such ascastor oil, phthalic acidesters etc. than is the case with hardenablecondensation products of the phenol or m-cresol, without the formationof turbidity (clouds) or exuding ening.

' Example 5 The phenol used according to Example 3 as starting materialis substituted by o-cresol. The condensation which takes placeconsiderably more slowly, is promoted by heating to C. The catalysts arefinally destroyed and eliminated by washing together with the hydrogenbromine I present in the reaction mixture.

50 grms. of l-methyl-l-cyclopentanol are shaken with three times thequantity of concentrated hydrogen chloride with initial cooling forabout 1 hour. 1 The tertiary methyl-cyclopentylchloride which has beenobtained almost quantitatively is separated-from the watery layer andcondensed with 43 grms. of phenol in the presence of 2 grms. ofaluminium chloride and an indif-.

ferent solvent at. room temperature for 24 hours.

After washing with water and distillation of the solvent 82 grms. of apale yellow raw product are obtained which solidifies in a crystallinestate and constitutes almost pure p-tertiarymethylcyclopentyl-phenol.

when condensing the product with formaldehyde almost colorlesslightprooi and readily oilsoluble resins are obtained. A resin havingdistinct hardenable properties is e. g. obtained, if the product offormaldehyde (40% vol.) with the aid of an amount of caustic lyesumcient forthe formation or aclear solution for 24 hours at 60 C.suitably in the presence of a reducing agent e. g. an

oxalate. The condensation product which is liquid above 60 C. isprecautiously freed from alkali by washing with weak acids and finallyshied.

during hardis condensed with an equal amount a If the condensation iscarried out at temperatures below 50 C. qily to viscous condensationproducts are obtained which may be converted into solid resins bysubsequent heating.

A phenolic body of lower uniformity and purity is obtained also in alower yield ="if' phenol is heated to about 110 C. immediately with thesaid alcohol in the presence of dehydrating agents e. g. zinc chloride,the reaction water being simultaneously distilled 011.

Example 7 100 parts of decahydronaphthalene (decalene) thinned with 3 to4 times the quantity of carbon tetrachloride, arechiorinated until theincrease in weight amounts to 50%. The mixture of the chlorides isgradually introduced with stirring into 100 parts of phenol at 50-60" C.in 'thepresence of 5 parts of zinc chloride. The condensation productwhich has been obtained with "splitting on of hydrogen chloride andwhich first is thickly liquid is converted by heating for several hoursat 100 C. andfby further splitting of! of hydrogen chloride into aresinous product which is solid at ordinary temperature.

After adding a water-insoluble thinning agent and removing the smallportion of phenol which has not entered into reaction by washing or thelike, the condensation is effected with 60 parts of formaldehyde '(40%-vol.) in the presence of 5 parts of concentrated hydrogen chloride withcontinuous stirring at boiling temperature. After removing the water,washing and distilling .oif

the thinning agent 165 parts of a pale-brown,

resin are obtained.

.Ekample 8 very hard. and high melting, readily oil-soluble phase in aniron tube at 600 C., and 50 grms. of a xylenol mixture boiling between207 and 217 C. are mixed and 3 grms. of aluminium chloride are graduallyadded. After the initially strong self-heating has abated the reactionmixture is heated for about 60 hours at 60 C. Thereafter it isfwashedwith-water and the portions of the mixture-of substances employed whichhave not taken part in the reaction are distilled off.

In this way 65 grms. of a mixture substantially consisting of benzeneand homologues and about 83 grms. of a residue of phenolic naturepartially consisting of slowly reacting xylenols are obtained. Accordingto statements in the literature apart from aromatic hydrocarbonsoleflnes, dioleflnes and a considerable portion of cyclic unsaturatedhydrocarbons having side chains are probably present in the initiallyapplied mixture of substances obtained from gas oil.

- The phenolic residue above obtained is con-, densed with 25 grms. offormaldehyde (40% vol.)

or l'l'grms. of acetaldehyde in presence of 4 grms.

of concentrated hydrochloric acid or other strong mineral acid. Veryhard and high melting, readily oil-soluble resins are obtained. Oilvarnishes prepared therefrom show a high resistance against alkalies.

\What we claim is:

1. A non-yellowing oondensation product obtained from formaldehyde andvl-ailryl-i-p-hydroxy-phenyl-cycioparafline.

2. A non-yellowing condensation product obtained from formaldehyde andl-methyl-l-p-hydroxy-phenyl cyclopentane.

3. A non-yel1owing condensation product obtained from formaldehyde andl-methyl-l-p-hydroxyphenyl-cyclohexane.

HERBERT 116mm. ALOIS ZINKE.

